Alkyd resins derived from cyclohexene oxide



Patented July 18, 1950 UNITED STATES PATENT OFFICE ALKYD RESINS DERIVEDFROM GYCLOHEXENE OXIDE Michel F. Cukier, New York, N. Y., assignor toPharma Chemical Corporation, New York,

N. Y., a corporation of New York No Drawing. Application May 4, 1945,Serial No. 592,060

4 Claims. (Cl. 26078.4)

My invention relates to new and valuable resins made by condensationsunder polymerizing conditions of polybasic acids, and polybasicanhydrides, with hydro-aromatic-ortho-diols, orhydro-aromatic-ortho-oxides, or mixtures thereof.

I have found that when a polybasic acid or anhydride like phthalic,maleic, iumaric, succinic, malic, malonic, citric, glycollic, tartaric.adipic, sebacic, azelaic, suberic, trimellitic, etc., is condensed withcyclohexene oxide or with any of the various possible forms of1.2-cyclohexanediol, or any mixture of these forms, or with a. I

on on o on 011 The words 1.2-cyclohexeneoxide" and cyclohexeneoxide" areused herein to designate the same chemical compound.

The graphic formula for cis-l-2-cyclohexane diol and fortrans-1-2-cyclohexanediol is CH OH-OH CH OH-OH The ratios of thecyclohexeneoxide or cyclohexanediol to the polybasic acid are usuallyequimolar, or, if desired, an excess of cyclohexeneoxide orcyclohexanediol may be employed.

These new resins range in consistency from soft to very hard and brittleand have good solubilities in organic solvents such as aliphatic andaromatic hydrocarbons, alcohols, ethers, ketones and hydrogenatedsolvents. Their acid numbers cover a wide range, depending on thepolybasic acid employed, the ratio of the cyclohexeneoxide orcyclohexanediol to the acid and the temperature and length of time ofheating.

Most of the straight resins, without any modi- 2 flcation, arecompatible with nitrocellulose lacquers and may be directly blended withthem.

The following are examples of processes for the production of some ofthe resins of my invention.

Example I 24.5 p. 1.2-cyclohexene oxide are mixed with 41.5 p. orthophthalic acid, and the mixture is heated, while stirring, to 30-40 C. Avery exothermic reaction takes place. When the temperature begins todrop, the liquefied product is heated during one hour to 220-230 C. andkept at this temperature for about two hours. The water liberated atthis temperature will gradually escape. The obtained resin is cooled andground. The resulting brittle resin is soluble in toluol,

hydrogenated mineral oils, mixtures of toluol and butyl acetate,acetone, ethyl alcohol, and in butyl. alcohol. The resulting resin hassimilar properties, even if a 20% excess of cyclohexene oxide is usedinstead of equimolar weights.

Example II.Succinic resin H- 0 O-OO--CH:-CH:CO-I on on on em cm 0 I H! a34.3 p. of 1.2-cyclohexeneoxide are mixed in a 3-neck flask, plunged inan oil bath with 41.3 p. of succinic acid, and the mixture is heated to85-95 C.

The exothermic reaction raises the temperature to about C. The liquefiedproduct is kept for a suitable time at .220-230 C. and treated as inExample I.

The resulting resin is somewhat soft and has properties similar to thephthalic resin.

Example III.--Maleic resin H- -O O--OCCH=CHC O OH CH CH CH: CH:

CH! OH! I 46.4 p. of maleic acid are charged in a 3-neck flask fittedwith an agitator and an air condenser.

39.2 p. of 1.2-cyc1ohexeneoxide are slowly added in small portions, thereaction being very exothermic.

When all oxide is added, the product is heated to 220-230 C. and ke t atthis temperature for about one hour.

The finished resin is very hard and transparent and possesses goodsolubilities in organic solvents.

Example IV.-Citric resin 57.6 p. of citric acid and 44.1 p. of1.2-cyclohexeneoxide are heated together at 220-230 C. The resultingresin has a marked trend toward the formation of filaments and fibers.

Because of possible cross linkings and interesteriflcation of the OHgroup of the citric acid. any stated formula would only beproblematical.

Example V.Phthalic resin 44.4 p. of phthalic anhydride are melted with38.38 p. of cis-cyclohexane-ortho-diol, CO, being Example W 38.4 p.citric acid anhydrous and 69.6 p. trans 1.2 cyclohexanediol M. P.99'-100 C. are heated together in a closed vessel, provided with astirring device, thermometer, tube for carbon dioxide gas, and an aircondenser, adjusted in order that the water formed during the reactionmay escape slowly. 'The reaction mixture is heated during one hour to185-190 C. under constant stirring and addition of carbon dioxide gas.The temperature is maintained at 190 C. for another three hours. Thenthe product is allowed to cool to 160 C. At this temperature 26 p.phthalic anhydride and 7 p. succinic anhydride are added and the mixtureheated to 2l5-220 C. during fifty minutes and kept at this temperaturefor about six hours. After pouring the molten mass on pans and cooling,a yellow, transparent, tough resin is obtained. The product is readilysoluble in butyl acetate, butyl alcohol, toluol, acetone, mixtures ofbutyl acetate and toluol, naphtha s01- vents, mixtures of benzol-ethylalcohol and is compatible with nitrocellulose lacquers.

Example VII 83 p. phthalic acid, 30 p. 1.2-cyclohexene oxide, 29 p."trans 1.2 cyclohexanediol (M. P. 99-100 C.) are heated together in theapparatus described in Example V1 for one hour to 225-230 C., whilecarbon dioxide gas is passed through the molten mass. After three hoursof heating at this temperature, a slightly brownish, hard, brittie resinis obtained. Its solubilities in organic solvents are similar to thoseof the resin in Example I.

Example VIII 60 p. maleic anhydride, 36.54 p. "cis" 1.2-cyclohexanediol(M. P. 104 0.), 36.54 p. "trans" 1.2- cyclohexanediol (M. P. 99-100 C.)are reacted together at 225-230 C. for about two hours. The productresulting from this condensation is similar to those mentioned for thereslnof Example III.

The following are mentioned from the aromatic dicarboxylic acids whichcan be successfully applied in my described process: phthalic acid,tetrahydrophthalic acid, diphenic acid, 1.8-naphthallc acid andcamphoric acid.

The following are mentioned from the aromatic tricarboxylic acids whichcan be used by replacing the equimolecular quantity in Example V andExample VIII: hemimellitic acid, trimellltic acid and pyromellitic acid.

It will be noted from the foregoing that my invention is directed to newsynthetic resins having valuable properties when employed alone and whenused in connection with compatible chemicals; and that the examples areset forth solely for the purpose of clearly defining my invention andthat, therefore, they are not a limitation as to the particularchemicals, quantities, temperatures, proportions or steps of procedurewithin the scope of my invention.

What I claim is:

1. Resins produced by the polymeric condensation of about 1 to 1.20 molsof 1:2-cyclohexene oxide with 1 mol of a dicarboxylic acid, in which thesole reactive groups are the respective carbcxylic acid and the 1:2epoxy groups, the said resins being soluble in toluol, hydrogenatedmineral oils, mixtures of toluol and butyl acetate, acetone, ethylalcohol, and butyl alcohol.

2. Resins of claim 1 in which the dicarboxylic acid is phthalic acid.

3. Resins of. claim 1 in which the dicarboxylic acid is succinic acid.

4. Resins of claim 1 in which the dicarboxylic acid is maleic acid.

MICHEL F. CUKIER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,860,098 Jaeger May 24, 19322,048,774 Bolton July 28, 1936 2,054,979 Jahrstorfer et al. Sept. 22,1936 2,056,656 Ellis Oct. 6, 1936 2,212,151 Coifman et a1. Aug. 20, 1940FOREIGN PATENTS Number Country Date 500,300 Great Britain May, 1938

1. RESINS PRODUCED BY THE POLYMERIC CONDENSATION OF ABOUT 1 TO 1.20 MOLSOF 1:2-CYCLOHEXENE OXIDE WITH 1 MOL OF A DICARBOXYLIC ACID, IN WHICH THESOLE REACTIVE GROUPS ARE THE RESPECTIVE CARBOXYLIC ACID AND THE 1:2EPOXY GROUPS, THE SAID RESINS BEING SOLUBLE IN TOLUOL, HYDROGENATEDMINERAL OILS, MIXTURES OF TOLUOL AND BUTYL ACETATE, ACETONE, ETHYLALCOHOL, AND BUTYL ALCOHOL.